Composition of matter and method of making the same



Patented Mar. 5, 1935 PATENT OFFICE COMPOSITION OF MATTER AND II'I'HOD OF MAKING THE Sm- Edwin R. Llttmann, Wilmington, Del, minor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware No Drawing. Application May 23, 1933, Serial 13 Claims.

This invention relates to a new composition of matter and method of producing and more particularly relates to a new class of esters produced in accordance with this invention by the esteriflcation of terpinene-maleic anhydride.

The esters embodying the invention are in general slightly yellow in color and may vary from viscous liquids to hard resinous solids depending on the alcohol employed. They have desirable characteristics such as light resistance and durability to a high degree and are adaptable for various uses. Thus, for example, the esters embodying this invention will be found to be soluble in various solvents, to be of desirable color, and to resist discoloration and weathering. Further, for example, the esters lend themselves to use as plasticizers or resins in nitrocellulose lacquers, the liquid esters in general having a distinct solvent power on nitrocellulose.

The esters embodying this invention may be produced by the esteriilcation of terpinene-maleic anhydride, the latter being readily prepared by reacting terpinene and maleic anhydride or equivalently maleic acid in the presence of heat, for example, as disclosed in the application for United States patent filed by Ernest G. Peterson and Edwin R. Littmann, Serial No. 496,560, filed November 18, 1930.

The esters maybe acid or neutral and may be prepared, and their preparation is contemplated, by various processes, as under atmospheric or other pressure, with and without the use of an esteriflcation catalyst, etc., etc. esters may be prepared with the use of various monohydric or polyhydric alcohols, aliphatic monohydric alcohols such as methyl, ethyl, butyl, n-propyl, isopropyl, bornyl, isobutyl, amyl, fenchyl, etc., alcohols, substituted aliphatic alcohols, such as benzyl alcohol, ethylene chlorohydrin, etc., etc., polyhydric alcohols such as ethylene glycol, propylene glycol, glycerol, pentaerythrite, etc., etc., and substituted polyhydric alcohols such as glycerol monochlorohydrin, glyceryl monoethvl ether, glyceryl monophenyl ether, etc., etc., are all contemplated within this invention.

If desired, in the production of the ester, an esterification catalyst may be employed and as such may be used, for example, sulphuric acid, dry hydrogen chloride, metallic zinc or tin, paratoluene sulphonic acid, etc., etc., and the esterification may be effected under atmospheric or other ressure.

As illustrative of the practical production of esters in accordance with this invention, using a monohydric alcohol, for example, the ester Further, the

In Germany May 3, 1932 diethyl-terpinene-maleate may be prepared by mixing say one mole, say 234g.ofterpinene-maleic anhydride withan excess of say ethyl alcohol, say 368 g. and adding as an esterification catalyst about 8% by weight or about g. of concena trated sulphuric acid. The mixture, of a light yellow color, is then kept at a gentle reflux, for say about 48 hours by, for example, heating. at a temperature of about C.

On completion of the heating period the result ant liquid is washed with water to remove the excess alcohol and sulphuric acid and then given an alkali wash, say with sodium carbonate solution, to remove any traces of sulphuric acid and any acid ester present. The product is then given I. a final water wash and the ester, which is a viscous liquid, is then dried say with anhydrous potassium carbonate.

If it be desired to further purify the ester, it may be distilled under reduced pressure, a part distilling at '195210 C. under a pressure of 15 mm. mercury. The residue which does not distill consists of the ester of the polymerized anhydride. Alternatively the ester may be refined by heating to a temperature of about C. and passing in air or some inert gas.

As further illustrating the production of the ester embodying this invention, for example, for the preparation of the ester dibutyl terpinenemaleate, say 234 g. of terpinene-maleic anhydride and 296 g. of butyl alcohol are mixed together, that is 4 mols. of butyl alcohol for each mol. of anhydride, and then heated for say '1 hours at a temperature of say 11'1" C., the boiling point of butyl alcohol. The reaction will result in the formation of mono-butyl terpinene-maleate which will be found to be a pale yellow, soft solid, which will remain dissolved in the excess alcohol. About 8% by weight of concentrated sulphuric acid is then added and the mixture is heated for approximately 40 hours at the same temperature, about 117 C. The result of the reaction will be the formation of dibutyl terpinene-maleate.

On completion of the heating period the reaction mixture is washed with water to remove the sulphuric acid. The excess butyl alcohol is then removed by distillation. If desired, the ester may be distilled imder reduced pressure for its purification or may be purified by air blowing at a temperature of approximately 150 C. It will be noted that volatile dibutyl terpinene-maleate distills at about 220 C.-240 C. under a pressure of 15 mm. mercury. The ester will be found to be slightly yellow in color and rather viscous. The residue remaining after the distillation of the volatile ester consists or the ester of the polymerized anhydride.

As illustrative of the practical adaptation of this invention, when a polyhydric alcohol for the esterification is employed a simple ester does not result. Polymerization takes place and the type of product formed is directly dependent on the alcohol employed as well as the temperature at which combination is allowed to take place. Thus, for example, when a dihydric alcohol is used, such as ethylene glycol, a hard resinous solid which is soluble in lacquer solvents results. when a polyhydric alcohol having more than two hydroxyl groups is used. on the other hand. the esterification it carried sufliciently far will lead to the formation of an insoluble gel. To avoid gelation it isnecessary to employ an excess of the polyhydric alcohol or to interrupt the reaction just as gelation is about to commence.

As illustrative of the practical adaptation of this invention with use of, for example, a dihydric alcohol, the esterification may be carried out with, for example, ethylene glycol as follows. Thus, for example, 270 parts by weight of terpinene-maleic anhydride and parts of ethylene glycol are heated together with good agitation at a temperature of 205-215 C. for approximately 8 hours. Excess glycol may be removed by applying reduced pressure. As a result of this treatment a hard, pale yellow, resinous solid is formed. It will be found to have an acid number of about 45 and a drop melting point of to C. It is soluble in organic solvents such as acetone, toluol, butyl acetate, etc., but is insoluble in alcohols.

Further, when a poly ydric alcohol such as glycerol, having three hydroxyl groups, is employed in the esterification, the esterification may be carried out in the following manner. Thus, for example, 300 parts by weight of terpinenemaleic anhydride and 100 parts by weight of glycerol are heated together with agitation at a temperature of -200 C. for 8 to 10 hours. After this heating the product is a pale yellow, hard and brittle resin having an acid number of about 75 and a drop melting point of 95 to 100 C. By continuing the heating, preferably in a thin layer, an insoluble and infusible product may be produced. Such a product is useful as a molding material.

The following example illustrates the method of carrying out the esterification with a substituted polyhydric alcohol, for example, one having the hydrogen of at least one hydroxyl group replaced by an alkyl or aryl radical to form an ether. Thus, for example, 23 parts by weight of terpinene-maleic anhydride and 13 parts of glyceryl monoethyl ether are heated together at a temperature of 220-230 C. for approximately 20 hours. The resulting product is a light yellow, soft resin, soluble in lacquer solvents and having an acid number of about 60 and a drop meltingpoint of 60 C.

The use of mixtures of more than one alcohol for the esterification is also contemplated. Thus, a monohydric alcohol such as butyl alcohol and a polyhydric alcohol such as glycerol may be used in combination to give mixed esters. The combination in such a case may be carried out in any manner such as partial esterification. first with butyl alcohol then completion of the esterification with glycerol, or vice versa.

It will be understood that the esters in accordance with this invention may be prepared by solvent.

various methods other than those specifically outlined above. For example, the production of the esters may be eifected at temperatures within the range of about 75 C. to 250 C. and the pressure may vary from atmospheric to about 300 pounds per square inch. The period required for esteriilcation will of course depend upon the temperature and pressure employed.

It will be understood that in accordance with this invention substituted monohydric and substituted polyhydric alcohols are contemplated as included as equivalents within the terms "monohydric and polyhydric alcohols as used in the claims appended hereto.

It will be understood that the esters in accordance with this invention will be found to possess various desirable characteristics and to be adaptable for various uses, such, for example, as an ingredient in lacquers, varnishes, and the like, together with the various well known ingredients thereof, as solvents, nitrocellulose, drying oils, plasticizers, gums, resins, etc., etc., and will be found especially adaptable for use as a plasticizer in connection with nitrocellulose lacquers in view of its excellent plasticizing properties and its properties as a solvent for nitrocellulose.

This application is a continuation in part of the application filed by Ernest G. Peterson and Edwin R. Littmann, Serial No. 560,052, filed August 28, 1931.

What I claim and desire to protect by Letters Patent is:

l. A reaction product of terpinene-maieic anhydride and an alcohol.

2. A reaction product of terpinene-maleic anhydride and an aliphatic alcohol.

3. A reaction product of terpinene-maleic anhydride and a monohydric alcohol.

4. A reaction product of terpinene-maleic anhydride and ethyl alcohol.

5. The method of producing a new composition of matter which includes reacting terpinenemaleic anhydride with an alcohol in the presence of an esterification catalyst.

6. The method of producing a new composition of matter, which includes reacting terpinenemaleic anhydride with an alcohol in the presence of heat.

7. The method of producing a new composition of matter, which includes reacting terpinenemaleic anhydride with an alcohol in the presence of heat and in the presence of an esterification catalyst.

8. A reaction product of terpinene-maleic anhydride and butyl alcohol. Y

9. A reaction product of terpinene-maleic anhydride and bornyl alcohol.

10. The method of producing a new composition of matter which includes reacting terpinenemaleic anhydride with a monohydric alcohol under pressure in the presence of heat.

11. A coating composition comprising a reaction product of terpinene-maleic anhydride and an alcohol, and a solvent.

12. A coating composition comprising a reaction product of terpinene-maleic anhydride and an alcohol, a non-volatile lacquer ingredient and a solvent.

13. A coating composition comprising a reaction product of terpinene-maleic anhydride and an alcohol, a non-volatile varnish ingredient and a EDWIN R. LI'I'I'MAN. 

